ABSTRACT A novel highly π-extended heteroarene Benzo[1,2-b:4,5-b’]di(naphtho[1,2-d]thiophene) (DBTBT) was used for organic field-effect transistors (OFETs). The mobilities of OFET were greatly improved from 0.34–0.58 cm2V−1s−1 to 1.02–1.75 cm2V−1s−1 by morphology tuning through 2 steps’ controlling substrate temperature. More importantly, the OFETs showed a good ambient stability in 30 days measurements. The flexible OFET arrays were prepared on polyethylene terephthalate substrate with octadecyl trichlorosilane modified polymethylsilsesquioxane/polyacrylonitrile gate dielectrics and demonstrated a 100% yield. Further, this flexible cell was used for ultraviolet light detection, which showed good ability of detecting low power light (such as λ = 254 nm, 7 μW/cm2).